Lubricating oil containing oil concentrate of an alkaline earth metal complex



United States Patent Ofitice 3,059,355 Patented Dec. 18, 19 32 3,069,355 LUBRICATING OIL CONTADHNG OIL CONCEN- OF AN ALKALINE EARTH METAL COM- L Herman D. Kluge, Kenneth L. Kreuz, and Morris A.

Wiley, Fishkill, N.Y., assignors to Texaco Inc., a corporation of Delaware No Drawing. Filed Feb. 9, 1959, Ser. No. 791,820 5 Claims. (Cl. 252-18) This invention relates to lubricating oil compositions having improved detergency. More particularly, this invention relates to lubricating oils incorporating minor amounts of a detergent composition comprising an oil concentrate of an alkaline earth metal complex.

The alkaline earth metal complexes of this invention are eifective detergents for crankcase lubricating oils employed in internal combustion engines. They are especially useful as alkaline components for cylinder lubricants for diesel engines operating on low quality distillate or residual fuels. Such fuels often contain high amounts of sulfur, vanadium and other materials normally corrosive to metal engine parts, particularly rings and liners.

in accordance with the present invention, the improved lubricating oil contains a detergent amount of an oil concentrate of an alkaline earth metal complex, said concentrate comprising mineral oil, from 0.1 to weight percent dispersed alkaline earth metal base consisting essentially of carbonate, from 1 to 40 weight percent alkaline earth metal salt selected from the group consisting of salts of oil-soluble sulfonic acids and salts of oil-soluble olefinphosphorus sulfide reaction products, and from 0.5 to 30 weight percent alkaline earth metal carboxylate in which additive a major portion of the metal carbonate component is formed by the decomposition of metal carboxylate and the total metal content is at least 2.0 weight percent and less than 15 weight percent.

'In the preferred form the concentrate detergent comprises a refined parafiin base distillate oil having an SUS viscosity at 210 F. of from 20 to 80, from about 3 to weight percent barium carboxylate, about 1 to 8 weight percent of basic barium compounds consisting essentially of barium carbonate of which at least a major portion was obtained by in situ decomposition of carboxylate, and from about 3 to 25 weight percent of an oil-soluble barium petroleum sultonate, the total metal content of the concentrate being from 3 to 12 weight percent.

The complex containing concentrate of this invention is usually added to lubricating oils in amounts ranging from 1 to 50 weight percent and preferably from 2 to weight percent depending on the degree of detergency desired.

The oil concentrates of alkaline earth metal complexes useful as detergents in accordance with this invention have been manufactured by processes disclosed in copending, coassigned applications, Ser. No. 645,667, filed March 13, 1957, now abandoned; Ser. No. 747,089, filed July 7, 1958; and Ser. No. 746,645, filed July 7, 1958. The methods of these applications are related. The method of application Ser. No. 645,667 broadly entails introducing a basic alkaline earth metal compound such as an oxide, hydroxide or carbonate of barium, calcium or strontium into a mineral oil, adding the dispersing agent to the oil and heating to specified temperatures while blowing with an oxidizing gas (air). The heating in this method is done in two temperature stages, the second stage being at least 50 and preferably about 100 F. higher than the first. The second stage heating should be carried out at a temperature of at least 400 F. and preferably 450- 550 P. which is about the decomposition temperature of the metal carboxylates which are formed by reaction between the basic alkaline earth metal compounds and the oil oxidation products.

in the method of application Ser. No. 747,089, the metal complex containing concentrate is formed by heating a metal carboxylate in the presence of basic reactin" inorganic metal compound and dispersant in a lubricating oil to a temperature between 400 and 850 F. preferably about 600 to 650 F. under non-oxidizing conditions for a period suflicient to form m tal carbonate by decomposition of a substantial portion of carboxylate. In the preferred form of this method, carboxylate and detergent are first formed in situ by heating a carboxylic acid material and a dispersant precursor acid in the presence of the basic metal compound to form salts.

The method of application Ser. No. 746,645 difiers from the last described method in that the metal carboxylate is oxidized to form the carbonate by blowing the mixture of carboxylate, detergent and. basic metal compound in a lubricating oil with an oxidizing gas (air) while heating to a temperature ranging from 325 to 550 F.

Each of the above described methods are excellent for producing the additive of the invention.

The mineral oil component of the additive of the invention can be a parafiin base, naphthene base or mixed base oil, however, a parafiin base oil is much preferred owing to the ease with which the additive is prepared when utilizing it. An example of a typical oil used in the additive of the invention is one prepared by distillation from a paraflin base crude followed by furfural refining, light acid treating, clay contacting, and solvent dewaxing. The characteristics of one particular oil refined in the above manner is as follows:

Viscosity, SUS at 210 F 54.0 Flash point, COC, F 44.0 Gravity, API 29.0

An example of the preparation of a. batch of the additive is as follows:

ADDITIVE PREPARATION The following ingredients were charged to a 20-barrel reaction kettle which Was heated by automatically controlled electrical heating coils. The kettle was equipped with an 82.5 r.p.m. mixer having an impeller diameter of 34 inches. Baffle plates were aifixed to the bottom of the kettle just outside the tips of the impeller blades. Air was caused to enter the kettle during the reacting period through two one-inch pipes with outlets diametrically opposed about 3 inches above the impeller blade tips. Spiral Water coils were installed in the kettle with neces sary instrumentation to measure water flow rate and record inlet and outlet temperature.

In the above description, the diametrically opposed air inlet pipes positioned above the impeller in the reaction kettle can be replaced by an air sparger for advantageous results.

3 These ingredients were reacted in the kettle under the following reaction conditions:

Time at 350 F. hours 5 Time for 350 F. to 450 F do 1 Time at 450 F. w./air do 1.3 Time at 450 F. w./N do 2.7 Air rate s.c.m.f 132 After completion of the reaction, the product had the following characteristics:

Barium content 8.9% (wt). Viscosity, at 100 F 362 s.s.U. 1:1 kerosene blend, CO percent 1.5 (approx).

Approximate percentages for the amount of the metal compounds of a barium complex-containing concentrate prepared as described above are as follows:

Percent wt.

Barium carbonate 8.7 Other basic barium compounds 2.3 Barium sulfonate 4.4 Barium carboxylate 7.3

It is often desirable to use the detergent of the invention in combination with other known detergents to meet the higher detergency requirements of heavy duty lubricating oils such as supplement one and series 11 lubricating oils.

For example, neutralized or basic alkaline earth metal sulfonates are excellent for obtaining higher levels of detergency in oil composition. The sulfonates include oilsoluble petroleum sulfonates and synthetic sulfonates such as alkyl aryl sulfonates derived from alkylated benzene or naphthenates. The sulfonates are added to the lubrieating compositions of the invention in amounts of from 0.5 to 5.0 wt. percent and preferably from 1.0 to 3.0%.

Another group of detergent compound which are advantageously added to lubricating compositions of this invention are the phenolates. The alkaline earth metal including the magnesium salts of alkyl phenols and sulfurized alkyl phenols, including CO neutralized sulfurized alkyl phenols, wherein the alkyl groups contain from 8 to 60 carbon atoms, are usually added to the lubricating compositions in amounts ranging from 0.5 to 5.0 wt. percent and preferably 1.0 to 3.0 wt. percent.

Still other excellent detergents for use with the metal complex detergent of the invention are the alkaline earth metal salts of reaction products of olefin polymers or copolymers with phosphorus pentasulfide wherein the olefin usually has from 2 to 10 carbon atoms and the polymers and copolymers thereof have molecular weights ranging from 400 to 10,000. A preferred product is one prepared using a polyisobutylene having a molecular weight ranging from 700 to 900. This detergent is usually used in amounts of from 2 to 6 weight percent and preferably in an amount ranging from 3.5 to 4.5 percent of the lubricating composition of the invention.

These described detergents in addition to lending additional detergency to the composition also have been found to prevent gelation of lubricating oil compositions containing larger amounts of the oil concentrate of alkaline earth metal complex of this invention when the compositions become contaminated with Water.

In lubricating oil compositions used under more stringent conditions such as the previously mentioned supplement one oils it is often desirable to include an oxidation inhibitor. Excellent antioxidants for this invention include metal dialkyl dithiophosphates having alkyl groups containing from 1 to 30 carbon atoms. This type of compound also lends anti-corrosive and extreme pressure properties to the oil composition. Dithiophosphates, particularly the calcium and zinc salts, are produced by the reaction of metal hydroxide, oxide or free metal with alkyldithiophosphates resulting from the reaction of monolaydroxy alcohols with phosphorus pentasulfide. Preferred alcohols are: methyl isobutyl carbinol, isopropyl alcohol, lauryl alcohol, cyclohexanol, methyl cyclohexanol and capryl alcohol. The preferred antioxidant is zinc dimethyl isobutyl carbinol dithiophosphate. These antioxidants are used in amounts ranging from 0.1 to 2.0 weight percent and preferably 0.5 to 1.0 percent in the lubricating composition.

Another excellent antioxidant particularly useful in lubricating oil compositions wherein zinc salts of dialkyl dithiophosphates are excluded owing to their detrimental effect upon silver bushings are the oil-soluble reaction products of terpehe with phosphorus pentasulfide (P 8 These oxidation inhibitors are the product of the reaction of dicyclic terpenes such as pinene, camphene and fenchene with phosphorus pentasulfide and are generally used in amounts ranging from 0.05 to 1.5 weight percent and preferably 0.2 to 1.0 percent of the lubricant composition. These reaction products are usually used in the form of hydrocarbon concentrates (50 percent) in order to facilitate handling.

Other antioxidants such as phenothi'azine and aromatic amines (diphenylamines, naphthylamines and phenylene diamines) are also useful components for compositions of this invention and are used in amounts ranging from 0.1 to 1.0 weight percent of the total composition.

Other additives or blend components may be added to the composition of the invention to further improve the lubricant qualities thereof. Viscosity index improvers such as the polymethacrylates are included. These methacrylate polymers are of the general formula CH2.C

wherein R is an aliphatic radical ranging from butyl to stearyl and n is an integer of more than 1. The polymers have molecular weights ranging from 500 to 10,000 and are used in the lubricating oil compositions in amounts ranging from about 1 to 20 wt. percent. The polymethacrylates are normally found as concentrates in mineral oil or synthetic oil carriers and are incorporated in lubricant compositions as such.

Foam inhibitors are usually incorporated in lubricating compositions of the present type. The silicone polymers, for example, dimethyl silicone, are extremely useful for this purpose and are usually incorporated in the lubricating oil compositions as hydrocarbon concentrates, generally kerosene, containing about 10% silicone. The concentrates are added in amounts ranging from 10 to 300 parts per million.

The lubricating oils which are useful base oils for the composition of the invention include hydrocarbon mineral oils and synthetic lubricating oils. Useful mineral oils are the paraffin base, naphthene base, mixed parafiin-naphthene base distillate or residual oils of lubricating viscosity.

The synthetic lubricating bases are usually of the ester or ether type. High molecular weight, high boiling liquid aliphatic dicarboxylic acid esters possess excellent viscosity-temperature relationships and lubricating properties, and are finding ever increasing utilization in lube oils adapted for high and low temperature lubrication; esters of this type are used in formulation of jet engine oils. Example of this class of synthetic lubricating bases are the diesters of acids such as sebacic, adipic, azelaic, alkenyl-succinic, etc.; specific examples of these diesters are di-Z-ethylhexyl sebacate, di-Z-ethylhexyl azelate, di2- ethylhexyl adipate, di-n-amyl sebacate, di-Z-ethylhexyl ndodecyl succinate, di-Z-ethoxyethyl sebacate, di-2-meth-. oxy-2-ethoxyethyl sebacate (the methyl Carbitol diester), di-Z'-ethyl-2-n-butoxyethyl sebacate (the Z-ethylbutyl ellosolve diester), di-Z-n-butoxyethyl azeletn (the m butyl Cellosolve diester), and di-2-n-butoxy-2-ethoxyethyl-n-octyl succinate (the n-butyl Carbitol diester).

Polyester lubricants formed by a reaction of an a1iphatic dicarboxylic acid of the type previously described, a glycol and a monofunctional aliphatic monohydroxy alcohol or an aliphatic monocarboxylic acid in specified mol ratios are also employed as the synthetic lubricating base in the compositions of this invention; polyesters of this type are described in US. 2,628,974. Polyesters formed by reaction of a mixture containing specified amounts of dipropylene glycol, sebacic acid and Z-ethylhexanol and of a mixture containing adipic acid, diethylene glycol and Z-ethylhexanoic acid illustrates this class of synthetic polyester lubricating bases.

Polyalkylene others as illustrated by polyglycols are also used as the lubricating base in the compositions of this invention. Polyethylene glycol, polypropylene glycol, polybutylene glycols and mixed polyethylene-polypropylene glycols are examples of this class of lubricating base.

The sulfur analogs of the above-described diesters, polyesters and polyalkylene others are also used in the formulation of the lubricating compositions of this invention. Dithioesters are exemplified by di-Z-ethylhexyl thiosebacate and di-n-octyl thioadipate; polyethylene thioglycol is an example of the sulfur analogs of the polyalkylene glycols; sulfur analogs of polyesters are exemplified by the reaction product of adipic acid; thioglycol and 2-ethylhexy1 mercaptan.

The lubricating oil compositions of this invention are useful in all types of internal combustion engines including spark ignition and compression ignition type engines. The compression ignition type includes marine diesel engines and railroad diesel engines which are run at both high and low speeds under heavy load.

Examples of various compositions of the invention are as follows:

Example I 77 weight percent.

23 Weight percent.

Example I] Base oil of Example I Concentrate of Example I Basic barium petroleum sulfonatcdimethyl silicone polymer in kerosene.-."

Example III Base oil similar to Example I having SUS viscosity at 210 F. of 68. Concentrate of Example I 82 weight percent. 16.75 weight percent. 1.25 weight percent. 50 p.p.m. (added).

56.3 weight percent.

43.7 weight percent.

Example IV Refined mixed paraifin-naphthene base oil having SUS viscosity at 210 F. of 79. Concentrate of Example I Basic barium petroleum sullonate Alpha-pinene-PrSs product (50% con 10% dimethyl silicone polymer in kerosene.-.

95.00 weight percent.

2.4 weight percent. 1.3 weight percent. 1.3 weight percent. 150 ppm. (added).

Example V Base oil similar to Example I having an SUS viscosity at 210 F. of 68.

Concentrate of Example I Basic barium petroleum sulfonate Example VI Refined paratlm base distillate oil having an SUS viscosity at 210 F. of 42. Concentrate of Example I Barium dinonylnaphthalene sulionate Zine di-methyl isobutylcarbinol dit phate. Pinene-PzS5 reaction product 0.30 Weight percent. 10% dimethyl silicone polymer in kerosene 50 p.p.m. (added).

64 weight percent.

33.5 weight percent. 2.5 weight percent.

87.25 weight percent.

8.4 Weight percent. 2.55 weight percent. phos- 0.5 weight percent.

0 Example VII Refined mixed paraiiin-naphtliene base having an SUS viscosity at 210 F. of 82. Concentrate of Example I Calcium sulfouate Barium allryl (Crow) phenolate sulfide..- Pinene-PQS reaction product 10% dimethyl silicone polymer in kerosene Example VIII oil 89.25 weight percent.

5.0 weight percent. 4.5 weight percent. 0.5 weight percent. 0.75 weight percent. ppm. (added).

82 weight percent.

15.50 weight percent 1.50 weight percent.

The lubricating oil compositions of this invention have been proven superior in a number of engine tests. The composition of Example I was tested in a Sigma P-l3 free-piston engine. This test is used to evaluate oncethrough lubricants for low speed marine diesel engines. This engine operates on the opposed piston two cycle principle, with two diesel pistons connected directly to compressor and bounce pistons. The engine is rated at 900-1000 strokes per minute with a maximum free air delivery of cubic feet per minute at 85 psi.

The results of the Sigma free-piston engine test on the lubricating oil composition of Example I and a number of other commercially available diesel lubricants are given in the following table wherein oil A is a homogeneous mineral oil containing about 3% of a mixture of about 65 percent neutralized basic barium sulfonate, 21 percent sulfurized barium salts of alkylated phenols and 13 percent zinc dialkyl dithiophosphate; oil B is a homogeneous mineral oil containing dispersed calcium acetate; and oil C is a homogeneous mineral oil containing about 29% calcium phenolate.

TABLE L-SIGMA FREE-PISTON ENGINE 1 Demerit ratings-diese1 pistons, Oil of Oil A Oil B Oil C Percent of max. example I Grooves 15 20. 5 26 25 Lands. 9. 1 25. 5 21. 1 15. 9 Skirts..." 0. 8 1. 2 2. 0 1. 35 crankcase l 0 4 1 Rocker Linkage..- 1 0 0 1 Ring Sticking 0 0 0 0 Ring Weight Loss, Diesel Pistons g./piston (5 rings):

Piston #1 0. 0003 0. 3019 0. 0750 0. 1014 Piston #2 0. 0124 0. 3626 O. 1574 0. 1202 Average 0. 0964 0.3323 0. 1165 0. 1138 1 50 hr. full load procedure.

The composition of Example I is also tested in the Nordberg diesel engine. The Nordberg diesel engine is a five cylinder (21.5 inch cylinder diameter) loop scavenged, tank type, two stroke diesel, burning bunker C type fuel containing 1.5 to 2.5% sulfur. Each cylinder has 6 lubricating quills and a different lubricant can be run in each of the five cylinders inasmuch as each cylinder has its own lubricant supply. The duration of the test is at the discretion of the company operating the englue and circumstances, e.g., mechanical failure will necessitate an earlier shutdown than possibly desired for economic reasons. In general, the elfectiveness of the lubricant is measured by the amount of wear on the cylinder liner and the rings. The cylinder liner diameter is measured before and after each test in 4 difierent directions in 5 different places: 2, 4 and 8 inches below top ring travel and 3 inches above and below the ports. The ring wear is measured by measuring the radial thickness of the ring in 5 places around the ring.

aoeaeea Results of this test are given in the following table: TABLE II.NORDBERG ENGINE TEST (1064 HRS.)

* Chrome plated liner. b New liner at start of test.

Comparison of wear rate data for liners 1, 2 and 4 and rings of pistons 1, 2, 4 and 5 show the following wear reductions for the lubricating oil composition of the invention over the inhibited lubricating oil used for comparison.

Liners: Percent Max. in any direction 64 Average at top ring travel 83 Average in combustion zone 74 Rings:

Max. at any point on ring 76 Average top ring wear 61 Results of the use of the compositions of Example I and Example 111 in the Nordberg engine test are given in the following table:

TABLE IIL-NORDBERG ENGINE TEST (1965 HRS.)

. 001 inch Summary of cylinder wear rates (1000 Lubricant Oil of Oil Oil of example I D 1 example III Cylinder No 1 2 4 5 Max. Wear 1. 5 3 4 1 1. 5 Avg. Wear Top Ring Travel 0. 75 1. 75 1. 25

1 Mineral oil composition containing chlorinated biphenyl.

The oil of Example III, as demonstrated by the above test data, lends improved wear protection over the oil of Example I. Piston ring wear by visual inspection was also less for cylinders 4 and 5 than in cylinders l and 2. This shows that the use of increased amounts of the detergent of the invention continues to improve performance of the oil. Amounts of the detergent complex containing concentrate over 50 percent of the oil composition become undesirable owing to a tendency to cause deposits in exhaust ports when used over the prescribed concentration.

The composition of Example IV was given exhaustive bench and engine tests to provide information with regard to its use as a heavy duty railway diesel oil suitable for use with economy diesel fuels. The composition of Example IV was subjected to the EMD (electromotive diesel) endurance test. This test consists of running a GM-567A electromotive diesel 6 cylinder engine utilizing the test lubricant and a high sulfur content economy diesel fuel under the following test conditions:

The data obtained as a result of testing in the EMD endurance test are set forth in the following table wherein oil E, an excellent diesel lubricating oil composition well tested in the field, consisted of a mixed paraffinnaphthene distillate oil having an SUS viscosity at 210 F. of 79.5 and a VI of and containing 5.0 wt. percent of a mixture of 8 parts calcium sulfonate with 2 parts barium alkylphenolate sulfide, 0.1 wt. percent sulfurized dipentene and 0.3 wt. percent phenyl alpha naphthylamine.

TABLE IV.END ENDURANCE TEST (600 HRS.)

Cleanliness demerit ratings Example Oil E IV, oil

Grooves, Compression 57 63 Grooves, Oil 1 5 Valves 1 12 Lands 60 53 5 0 Air ports 2 21 Piston skirts 43 Liners 11 14 Crankmqe 1 3 Air hnxns 2 A; Top decks 1 4 The above data indicate that the detergent of the invention lends exceptional cleanliness properties to the base oil when compared with a diesel lubricating oil known to give excellent performance in the field with economy fuels.

In the well known MacCoull corrosion test the lubricant of Example IV also showed its excellence. These tests are set forth in the following table:

TABLE V.-MACCOULL CORROSION TEST Example Oil E IV, oil

Bearing weight loss (10 Hrs.) 14, 18 24, 54 Neut. No. (Salt) 3. 9 4. 0 Visc. Increase at F., percent- 63 56 The oxidation stability of the oil containing the complex containing concentrate of the invention is well demonstrated.

As previously stated the invention also includes the further improvement of stabilizing the lubricating oil composition against gelation when higher amounts of the complex detergent of the invention are used in compositions which become contaminated with water. This invention entails the incorporation of from 0.5 to 6 wt. percent of an additional amount of the previously described detergent salts. These salts include petroleum and synthetic sulfonates, alkyl phenolates and CO neutralized sulfurized alkyl phenolates, and salts of olefin polymer-P 8 reaction products.

The ability of the detergents, as represented by basic barium sulfonate, to prevent gelation of the oil composition in the presence of water is demonstrated by the results of the water gelling test on various lubricating oil compositions. In this test, two 100 ml. samples of the test oil are mixed with 0.5 and 5 ml. respectively of distilled water and stirred with a mechanical stirrer for three minutes at 900 rpm. The condition of the samples after standing for 1, 3 and 24 hours is observed.

The base oils in the following table are highly refined petroleum oils having SUS viscosities at 210 F. of 66 to 81.

TABLE VI.--\VATER GELLING (1) Base oil+23 wt. percent complex detergent cone. (2) Base oil+16.75 wt. percent complex detergent conc.+1.25 wt, percent basic barium sulfonate (3) Base oil+-13.7 wt. percent complex detergent cone. (4) Base oi1+33.5 wt. percent complex detergent eonc.+2.5 wt. percent basic barium sulfonate 25) 100% complex detergent cone.

TEST

Sometimes fails.

Always passes.

Always fails.

Always passes. Always fails.

Always passes.

It is obvious from the above table that the complex detergent containing base oil which tends to gell under the test conditions is stabilized by the addition of minor amounts of the sulfonate detergent which also advantageously produces additional detergency. The amount of complex detergent concentrate which will cause gelling in the presence of water varies somewhat in each case depending on uncontrolled additive production variability. Some additive batches may cause gelling at 15-20 percent addition while others will not produce gelling until as much as 30 percent concentrate is blended with the base oil. However, generally, from 20 to 25 wt. percent of the complex detergent concentrate is usually border-line in causing gelation of the lubricating oil. Therefore, when using these higher amounts of complex, containing concentrate it is extremely desirable, if not necessary, to incorporate from 0.5 to wt. percent additional detergent in the composition.

Obviously many modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof and, therefore, only such limitations should be imposed as are indicated in the appended claims.

We claim:

1. A lubricating composition consisting essentially of a lubricating oil, l550 percent by weight of a detergent concentrate consisting essentially of a mineral lubricating oil containing 3-40 percent by weight of a dispersant selected from the group consisting of alkaline earth metal salts of oil-soluble sulfonic acids and alkaline earth metal salts of oil-soluble olefin-phosphorus sulfide reaction products, 350 percent by weight of a higher aliphatic alkaline earth metal corboxylate and 1-15 percent by weight of a dispersed alkaline earth metal base consisting essentially of carbonate, the total metal content of the said detergent concentrate being at least 2.0 percent by weight and less than 15 percent by weight, and about 0.5-6 percent by Weight of an additional detergent selected from the group consisting of alkaline earth metal salts of oil-soluble sulfonic acids, alkyl (C phenols, alkyl (C phenol sulfides and reaction products of phosphorus pentasulfide with olefin (C polymers having molecular weights in th range 400-10000, said detergent concentrate being obtained by decarboxylating an alkaline earth metal carboxylate to form the said metal carbonate in the presence of the said mineral lubricating oil containing alkaline earth metal base and the said dispersant, said lubricating composition without the said additional detergent forming gels in the presence of water and said composition containing the said additional detergent being non-gelling in the presence of water.

2. The lubricating composition of claim 1 wherein the said additional detergent is a basic alkaline earth metal sulfonate.

3. The lubricating composition of claim 1 containing 0.05-l.5 percent by weight of an oil-soluble anti-oxidant reaction product of a dicyclic terpene and phosphorus pentasulfide.

4. The lubricating composition of claim 1 wherein the said alkaline earth metal is barium.

5. The lubricating composition of claim 1 wherein the said detergent concentrate is obtained by air blowing a mixture of parafiinic lubricating oil, barium sulfonate and barium oxide at a temperature in about the range 325550 F.

References Cited in the file of this patent UNITED STATES PATENTS 2,316,080 Loane et a1 Apr. 6, 1943 2,417,428 McLennan Mar. 18, 1847 2,739,124 Otto et a1. Mar. 20, 1956 2,739,125 Myers et a1 Mar. 20, 1956 2,763,615 Faust Sept. 18, 1956 2,916,451 Faust Dec. 8, 1959 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Nos 3,069,355 December 18, 1962 Herman D, Kluge et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 9, line 32, for "'350" read 3-=3O column 10, line 5, for "th" read the 'a Signed and sealed this 11th day of June 1965o (SEAL) Attest:

ERNEST w. SWIDER DAVID LADD Attesting Officer Commissioner of Patents 

1. A LUBRICATING COMPOSITION CONSISTING ESSENTIALLY OF A LUBRICATING OIL, 15-50 PERCENT BY WEIGHT OF A DETERGENT CONCENTRATE CONSISTING ESSENTIALLY OF A MINERAL LUBRICATING OIL CONTAINING 3-40 PERCENT WEIGHT OF A DISPERSANT SELECTED FROM THE GROUP CONSISTING OF ALKALINE EARTH METAL SALTS OF OIL-SOLUBLE SULFONIC ACIDS AND ALKALINE EARTH METAL SALTS OF OIL-SOLUBLE OILFIN-PHOSPHORUS SULFIDE REACTION PRODUCTS, 3-50 PERCENT BY WEIGHT OF A HIGER ALIPHATIC ALKALINE EARTH METAL CARBOXYLATE AND 1-15 PERCENT BY WEIGHT OF DISPERSED ALKALINE EARTH METAL BASE CONSISTING ESSENTIALLY OF CARBONATE, THE TOTAL METAL CONTENT OF THE SAID DETERGENT CONCENTRATE BEING AT LEAST 2.0 PERCENT OF THE WEIGHT AND LESS THAN 15 PERCENT BY WEIGHT, AND ABOUT 0.5-6 PERCENT BY WEIGHT OF AN ADDITIONAL DETERGENT SELECTED FROM THE GROUP CONSISTING OF ALKALINE EARTH METAL SALTS OF OIL-SOLUBLE SULFONIC ACIDS, ALKYL (C8-60) PHENOLS, ALKYL (C8-60) PHENOL SULFIDES AND REACTION PRODUCT OF PHOSPHROUS PENTASULFIDE WITH OLEFIN (C2-10) POLYMERS HAVING MOLECULAR WEIGHTS IN THE RANGE 400-10,000, SAID DETERGENT CONCENTRATE BEING OBTAINED BY DECARBOXYLATING AN ALKALINE EARTH METAL CARBOXYLATE TO FORM THE SAID METAL CARBONATE IN THE PRESENCE OF THE SAID MINERAL LUBRICATING OIL CONTAINING ALKALINE EARTH METAL BASE AND THE SAID DISPERSANT, SAID LUBRICATING COMPOSITION WITHOUT THE SAID ADDITIONAL DETERGENT FORMING GELS IN THE PRESENCE OF WATER SAID COMPOSITION CONTAINING THE SAID ADDITIONAL DETERGENT BEING NON-GELLING IN THE PRESENCE OF WATER. 